RESEARCH ON TI(CF3SO3)4 .1. SYNTHESIS AND STRUCTURAL-ANALYSIS OF COMPOUNDS FROM REACTIONS OF CF3SO3H WITH TICL4, TI(NO3)4 AND TI(CLO4)4 AND REACTIONS OF NO2CF3SO3 WITH TICL4 AND REACTIONS OF (CF3SO2)2O WITH TI(OC2H5)4

By reacting HOTf (OTf = CF3SO3) with TiCl4, Ti(NO3)4, and Ti(ClO4)4; NO2OTf with TiCl4; and (CF3SO2)2O with Ti(OEt)4, the following molecules can be prepared: TiCl3OTf, TiCl2(OTf)2, TiCl0.75(OTf)3.25, [(NO2)2Ti(OTf)6] and Ti(OEt)2(OTf)2. Thermal degradation of some of these products leads to oxo complexes such as [(NO2)(NO)][TiO(OTf)4], [NO]0.75[TiO0.625(OTf)3.5] and TiOx(OTf)y. The IR and Raman spectra for TiClx(OTf)y complexes are consistent with previous results. In TiCl3OTf, the OTf group is tridentate whilst it is bidentate and bridging in the two other chloro complexes. TiOx(OTf)y and Ti(OEt)2(OTf)2 are polymeric molecules with monodentate and (or) bridging bidentate OTf groups and TiOTi bridges in the oxo complexes. In the nitryl or (and) nitrosyl salts, OTf is monodentate. [Ti(OTf)6(2-)] is monomeric while the other anions are polymeric with TiOTi bridges.